用稳定同位素取代的DL-阿比糖：合成、核磁共振光谱分析及呋喃糖异头物异构化

DL-apiose substituted with stable isotopes: synthesis, n.m.r.-spectral analysis, and furanose anomerization.

作者信息

Snyder J R, Serianni A S

机构信息

Department of Chemistry, University of Notre Dame, Indiana 46556.

出版信息

Carbohydr Res. 1987 Aug 15;166(1):85-99. doi: 10.1016/0008-6215(87)80046-0.

DOI:10.1016/0008-6215(87)80046-0

PMID:3308088

Abstract

The branched-chain pentose DL-apiose has been synthesized in good yield by a new and simple chemical method that can be adapted to prepare (1-13C)-, (2-13C)-, (1-2H)- and/or (2-2H)-enriched derivatives. N.m.r. spectra (1H- and 13C-) have been interpreted with the aid of selective (13C)- and (2H)-enrichment, and 2D and 13C[13C]-n.m.r. spectra. The solution composition of DL-(1-13C)apiose in 2H2O, determined by 13C-n.m.r. spectroscopy, has been found to differ from that determined previously by 1H-n.m.r. spectroscopy. Several 13C-1H and 13C-13C couplings have been measured and interpreted in terms of apiofuranose ring conformation. Ring-opening rate-constants of the four apiofuranoses [3-C-(hydroxymethyl)-alpha- and -beta-D-erythrofuranose, and 3-C-(hydroxymethyl)-alpha- and -beta-L-threofuranose] have been determined by 13C-saturation-transfer n.m.r. spectroscopy, and compared to those obtained previously for the structurally related tetrofuranoses.

摘要

支链戊糖DL-阿比糖已通过一种新的简单化学方法以高收率合成，该方法可用于制备富含(1-¹³C)-、(2-¹³C)-、(1-²H)-和/或(2-²H)的衍生物。借助选择性(¹³C)-和(²H)-富集以及二维和¹³C[¹³C]-核磁共振谱对核磁共振谱(¹H-和¹³C-)进行了解析。通过¹³C-核磁共振光谱法测定，发现DL-(1-¹³C)阿比糖在重水中的溶液组成与先前通过¹H-核磁共振光谱法测定的结果不同。测量了几个¹³C-¹H和¹³C-¹³C耦合，并根据阿比呋喃糖环构象进行了解释。通过¹³C饱和转移核磁共振光谱法测定了四种阿比呋喃糖[3-C-(羟甲基)-α-和-β-D-赤藓呋喃糖，以及3-C-(羟甲基)-α-和-β-L-苏阿糖]的开环速率常数，并与先前获得的结构相关的四氢呋喃糖的开环速率常数进行了比较。